NZ199281A - Production of an ether from an olefin and an alcohol using zeolite catalyst - Google Patents
Production of an ether from an olefin and an alcohol using zeolite catalystInfo
- Publication number
- NZ199281A NZ199281A NZ199281A NZ19928181A NZ199281A NZ 199281 A NZ199281 A NZ 199281A NZ 199281 A NZ199281 A NZ 199281A NZ 19928181 A NZ19928181 A NZ 19928181A NZ 199281 A NZ199281 A NZ 199281A
- Authority
- NZ
- New Zealand
- Prior art keywords
- zeolite
- process according
- alcohol
- olefin
- zeolites
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
- B01J2229/123—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation in order to deactivate outer surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
Abstract
A process for the production of an ether by contacting an olefin and an alcohol with a catalyst comprising a zeolite having an XO2/Y2O3 ratio equal to or greater than 10, wherein X is silicon and/or germanium and Y is one or more of aluminium, iron, chromium, vanadium, molybdenum, arsenic, manganese, gallium or boron, the zeolite being predominantly in the hydrogen form. The process is particularly suitable for the production of methyl t-butyl ether from isobutene and methanol.
Description
New Zealand Paient Spedficaiion for Paient Number 1 99281
19 9281
Priority Date(s): (9..'/.$Qt
Complete Specification Filed: /SrJ.^W Cisss: .
Publication Date:
P.O. Journal, fsio:
NO
pwg f
NEW ZEALAND
No.: Date:
PATENTS ACT, 1953
COMPLETE SPECIFICATION
C!;7, (PAfSW C5-a;:A„
PRODUCTION OF ETHERS
x*/ We, IMPERIAL CHEMICAL INDUSTRIES PLC of Imperial Chemical House, Millbank, London, SW1P 3JF, England, a British Company hereby declare the invention for which we pray that a patent may be granted to OCX/us, and the method by which it is to be performed, to be particularly described in and by the following statement: -
- 1 - (followed by page la)
le^
9928
Production o£ Ethocs
The present invention relates to the production of ethers, especially tertiary alkyl ethers.
It is known to produce ethers by reacting olefins and alcohols in the presence of suitable catalysts. For 5 example, tertiary alkyl ethers may be prepared by reacting a tertiary olefin and an alcohol, e.g. isobutene and methanol to give methyl t-butyl ether, in the presence of catalysts such as mineral acids, e.g. sulphuric acid, and a range of solid catalysts such as heteropolytungstic or 10 molybdic acids doped with phosphorus or boron, acidified alumina, and various acidified ion-exchange resins.
The use of mineral acid catalysts can give rise to corrosion problems which make it difficult to apply such catalysts on a commercial scale. Commercial pro-15 cesses are known using acidified ion-exchange catalysts, especially for the production of methyl t-butyl ether, which is particularly useful as a gasoline additive with high octane properties, but such catalysts often have poor thermal stability and this limits the 20 reaction temperature which can be used, e.g. in many
1 9 92 8 f
2
cases reaction temperatures not in excess of 80°C. The use of lower reaction temperatures can in turn result in long reaction times and low throughput per unit volume of reaction vessel.
Another problem which can arise with known pro cesses is the formation of dialkyl ether by-products deriving from the alcohol used.
Polish Patent No. 103379 describes a method of making methyl t-butyl ether by reacting methanol and 10 isobutene in the presence of a catalyst comprising zeolite X or Y or a partially dealuminated, modified or ion-exchanged form thereof, the process being carried out in a vapour or liquid phase. Using zeolite Y in a vapour phase process at 120°C, a liquid product is obtained con-15 sisting of 8.1% methyl t-butyl ether and 91.8% methanol. The same zeolite is used in a liquid phase process at 160°C and a pressure of 31 atmospheres and a partially dealuminated zeolite Y is used at 125°C and a. pressure of 23 atmospheres.
According to US Patent No. 2882244, zeolite X has a silica/alumina ratio in the range 2-3 and according to US Patent No 3130007, zeolite Y has a silica/alumina ratio in the range 3-6.
We have now found that tertiary alkyl ethers may 25 be prepared from tertiary olefins and alcohols in the presence of certain zeolite catalysts under milder con- : ditions than are described in the Polish patent, conditions which allow the production of the tertiary alkyl ethers at high selectivity and in good yield, with low 30 yields of undesirable by-product dialkyl ethers and oligomers of the olefin.
According to the present invention we provide a process for the production of an ether which comprises contacting an olefin and an alcohol with a catalyst com-35 prising a zeolite having an XO2/Y2O3 ratio equal to or greater than 10, wherein X is silicon and/or germanium,
3
I392SI
and Y is one or more of aluminium, iron, chromium, vanadium, molybdenum, arsenic, manganese, gallium or boron, the zeolite being predominantly in the hydrogen form.
The said zeolites have acid sites within zeolite pore systems active in the catalysis of tertiary alkyl ether formation. The entry port size in the preferred zeolites is such that reactants and products can move into and out of the pore systems, i.e. with a Lennard 10 Jones diameter a (A) of from about 5.0 to 8.0 iP (the
Lennard Jones diameter a (A) is defined by D W Breck in "Zeolite Molecular Sieves", Wiley Interscience, 1947, page 636).
The preferred zeolites for use as catalyst are 15 based on XO2 as silica (Si02) and Y2O3 as alumina (A1203) Suitable zeolites which may be employed as catalysts in the process of the invention include:
Zeolite beta (US 3308069)
ZSM-5 (US 3702886)
ZSM-8 (UK 1334243)
ZSM-11 (US 3709979)
ZSM-12 (US 3832449; EPA 0013630)
ZSM-23 (US 4076842)
ZSM-35 (US 4016245)
ZSM-43 (EPA 0001695)
ZSM-48 (EPA 0015132)
FU-1 (UK 1563346)
FU-9 (NZ 199282)
Nu-2 (NZ 199283)
Nu-4 (NZ 200677)
Nu-5 (NZ 199278)
Nu-6(2) (NZ 199112)
Nu-10 (NZ 200678)
EU-1 (European Appln,
EU-2 (NZ 197291)
81302343.9)
: \; 151
19928)
4
Zeolite omega Zeolite phi
(UK 1178186)
(US 4124686)
The zeolites may be converted to their hydrogen form by methods which have been fully described in the prior art, for example by calcination of the as-made zeolite and subsequent acid exchange. If desired, the zeolites may be ion-exchanged or impregnated so as to comprise cations or oxides selected from the following, Cu, Ag, Mg, Ca, Sr, Zn, Cd, B, Al, Sn, Pb, V, P, Sb, Or, Mo, W, Mn, Re, Fe, Co, Ni, noble metals and lanthanides. The formation of olefin oligomers may be further inhibited by treating the zeolite with a bulky-organic base, for example phenanthridine. It is believed that the base neutralises the surface acidic sites whilst being unable, because of its bulk, to enter the pore system of the zeolite.
Suitable olefins for use in the process of the invention include mono- or di-olefins containing from 4-16 carbon atoms, especially 4 to 9 carbon atoms, e.g. isobutene, 2-methylbut-l-ene, 2-methylbut-2-ene, 2-methylpent-l-ene, 2-methylpent-2-ene, 3-methylpent-2-ene, 2-methylhex-l-ene, 2-methylhept-l-ene and 2-methyloct-l-ene, or mixtures thereof.
Suitable alcohols for use in the process of the invention include primary and secondary alkanols containing from 1 to 12 carbon atoms, more preferably containing from 1 to 4 carbon atoms, e.g. methanol, ethanol, n-propanol, iso-propanol, and n-butanol. Also included are ether alcohols, e.g. ROfCI^CI^O^H where R is H or hydrocarbyl and n is 1-20, e.g. 2-methoxyethanol.
The process of the invention is particularly applicable to the production of tertiary alkyl ethers containing a total of 5 to 10 carbon atoms from the corresponding tertiary olefins and alcohols, and especially to the production of methyl t-butyl ether
from isobutene and methanol. The preferred zeolite catalysts for use in the production of MTBE are zeolites Nu-2, Nu-4, Nu-10 and beta.
The etherification reaction may be carried out in 5 the vapour or liquid phase. The liquid phase reaction is typically carried out in a stirred and heated pressure vessel containing the reactants and catalyst. In the gas phase, the reactants may conveniently be passed through a heated tubular reactor containing the catalyst. This .10. process readily lends itself to continuous production of the ether product.
The liquid phase and vapour phase processes may suitably be carried out at a temperature in the range from 0°C to 200°C, preferably in the range from 50°C to 15 110°C, for example 70°C to 100°C. The reaction is normally conducted under atmospheric or superatmospheric pressure, e.g. at a pressure in the range 1 to 100 bars.
The molar ratio of the olefin to alcohol may vary widely but is suitably in the range from 0.5 to 5.0 moles 20 of alkanol per mole of olefin.
For the liquid phase process, the proportion of catalyst in the reaction mixture may vary within very broad limits, but is suitably within the range from about 0.1 to about 5% by weight.
Under conditions suitable for the reaction of an alkanol and an olefin to yield tertiary alkyl-ethers selectively, the zeolite catalyst is remarkably stable and does not itself suffer damage from degradation reactions which give materials having poor catalytic 30 activity. By virtue of its nature,a zeolite can be rapidly recovered from the reaction mixture in liquid phase processes and can be reused in further batch operations.
Zeolites for use in. the process of the invention, 35 and methods for their preparation, have been described in the patent specifications referred to above. Inasmuch
6
as some of these patent specifications are as yet unpublished, further details of zeolites Nu-2, Nu-4, Nu-5, Nu-6, Nu-10, EU-1, EU-2 and FU-9 are provided below.
Zeolite Nu-2 has a molar composition expressed 5 by the formula:
0.5 to 1.8 R2O : Y203 : at least 10 X02 : 0 to 100 H20 wherein R is a monovalent cation or 1/n of a cation of valency n, X is silicon and/or germanium, Y is one or more of aluminium, iron, chromium, vanadium, molybdenum, 10 arsenic, manganese, gallium or boron, and H2O is water of hydration additional to water notionally present when R is H, and has an X-ray pattern substantially as set out in Tables 1 and 2 (as determined by standard technique using copper Ka radiation). Table 1 shows X-ray data for 15 zeolite Nu-2 as prepared, and Table 2 shows X-ray data for zeolite Nu-2 in the calcined Na-H form.
Within the above definition of chemical composition, the number of moles of X02 is typically in the range 10 to 100 and. zeolite Nu-2 appears to be most readily formed in 20 a state of high purity when the number of moles of X02 is in the range 25 to 50.
Zeolite Nu-2 may be prepared by reacting an aqueous mixture containing at least one oxide X02, at least one oxide Y203, and at least one alkylated or partially 25 alkylated quaternary ammonium or phosphonium or ternary sulphonium compound i.e. (R^R2R3R4N)+ or (R2R2R3R4P)+ or (R1R2R3S)+ hereinafter referred to as Q+. R^, R2, R^
and R^ can be from two to four ethyl groups, the remainder can be H, CH3 or C^H^. Alternatively precursors of the 30 quaternary compound can be used e.g. triethylamine plus ethanol, or an ethyl halide or sulphate, in which case the precursor is preferably preheated in a solvent e.g. methyl ethyl ketone, prior to the addition of other reactants.
The reaction mixtures preferably have the fol lowing molar composition.
X02/Y203 ^ 10, preferably 10 to 3000
TABLE 1
Zeolite Nu-2 as made dA
11. 33
9.04
7.56
6.61
6.03
.37
4.51
4. 14
3.96
3.51
3.46
1001/ lo
23 vb
3
4 vb
3
3 vb
vb
2
23
100 vb*
12
3
dA
3. 38
3.31
3.10
3.02
2.93
2.91
2.68
2.59
100/1 lo
2
21
7vb
21
8
5vb
6
3
Vb = very broad diffraction peak
Vb* = very broad base but terminating in a very sharp peak TABLE 2
Calcined sodium hydrogen Nu-2
dA
11.33
9.04
7.56
6.61
6.03
.37
4.51
4.14
3.96
3.51
3.46
1001/ lo
22vb
17.5
4vb
3
3vb
0
2
12
100 vb*
12
3
dA
3.38
3.31
3.10
3.02
2.93
2.91
2.68
2.59
1001/ lo
2
7vb
12
3
5vb
6
2
8
Ak+/Q+ = 0.15 to 2.0 H20/QZ =30-75 0H-/X02 = 0.1 to 2.0 H20/Ak+ > 15 5 QZ/X02 = 0.02 to 0.4
wherein X and Y are as above, Ak+ is an alkali metal ion, or mixtures of such ions, which can include ammonium, and refers to free alkali, 0H~ includes free alkali and free quaternary ammonium hydroxide and Z is OH or any 10 acid radical. When Z is an acid radical an equivalent excess of free Ak+ must be added as hydroxide in order to maintain the alkalinity of the reaction mixture. Q+ is a quaternary ion of N, P or S.
The preferred quaternary compound is tetra-15 ethylammonium hydroxide.
Zeolite Nu-4 has a molar composition expressed by the formula:
to 15 M^O : 0 to 10 Y203 : 100 X02 : 0 to 50 H20
wherein M"*" is a monovalent cation or 1/n 'of a cation of valency n, X is silicon or germanium, Y is aluminium,
iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese, gallium or boron, and H~0 is water of hydration
^ l additional, to water notionally present when M is H, and 25 has an X-ray pattern substantially as set out in Table 3 (as determined by standard technique using copper Ka radiation). Table 3 shows X-ray data for zeolite Nu-4 as prepared and in the calcined hydrogen form.
Within the above definition of chemical com-30 position, the number of moles of Y203 is typically in the range 0 to 10 and zeolite Nu-4 appears to be most readily formed in a state of high purity when the number of moles of Y203 is in the range 0 to 4.
Zeolite Nu-4 may be prepared by reacting an 35 aqueous mixture comprising at least one oxide X02, at least one oxide Y203 and at least one polyalkylene
9
TABLE 3
Zeolite dA
Nu-4
(as made) 100 I/I0
Zeolite Nu-4
(calcined H form) dA 100 I/I0
11.3
16
-
-
11.1
11.07
33
.08
.07
36
9.90
8
9.96
9.7?
6
9.79
-
-
9.28
1
9.05
1
9.02
1.5
-
-
8.08
1
7.50
2
7.45
4
7.09
1
7.09
2
6.78
2
6.72
4
6.44
6.38
8
6.07
4
6.08
6.05
6.02
7
.97
1
.99
7
.75
8
.73
9
.65
6
.57
8
.63
2
-
-
.41
2
.38
2
.19
2
.15
4
.07
2
.04
3
.01
4
.005
4.915
1
4.899
1
-
-
4.725
1
4.639
9
4.610
9
4.018
1
4.5ml
1
4.495
2
4.490
I
4.475
2
4.470
2
4.386
13
4.380
14
4.291
4.280
13
4.124
13
4.103
3
4.104
4
-
-
4.039
6
4.022
7
3.9SO
1
3.950
2
3.880
100
-
-
3.850
69
3.869
100
-
-
3.836
73
3.743
51
3.764
3.730
50
3.735
54
3.678
27
3.662
29
3.649
22
3.604 •>
4
3.629
-
-
-
-
3.500
3.466
12
3.469
3.364
6
3.368
7
3.332
9
3.342
3.329
4
-
3.273
4
3.265
3
3.267
4
-
-
3.260
4
3.260
12
<o) (c$\ 6> ^
polyamine having the formula:
*2
N — [ (CH2) —N - R3 ] y (CH2) N
where x is in the range 2 to 6 and y is in the range from 0 to 10, an amine degradation product thereof, or a precursor thereof. In the polyamine, each of to Rg, independently, represents hydrogen or a C^-Cg alky group. When y is from 2 to 6, the R^ substituents may be the same or different. When y = 0 then x = 2 to 5.
The reaction mixture can have the following molar ratios:
xo2/y2o3 ^ 10
= 0.01 to 4.0 = 0 to 2.0 = 10 to 200 = 0 to 4.0
Q/xo2 MI0H/X02 h2o/xo2 m2z/x02
wherein x and Y are as above, is an alkali metal or
2
ammonium or hydrogen, M is an alkali metal or ammonium or hydrogen and can be the same as M^" and Q is the aforesaid polyalkylene polyamine, amine degradation product thereof or a precursor thereof, or a related compound. Z~ is a strong acid radical present as a salt of and may be added as a free acid to reduce the free M-^-OH level to a desired value. However, zeolite Nu-10 can be synthesised from a narrow range of molar ratios which falls within this much wider range for zeolite Nu-4 synthesis. Therefore if Si02/Al203 ratios between 70 and 300 are chosen, then to ensure that zeolite Nu-4 is obtained free of zeolite-Nu-10 it is necessary to employ
1 f 92
11
either low H20/X02 ratios or high M^0H/X02 ratios or both.
The preferred ranges for preparing zeolite Nu-4 are as follows:
Range 1
x02/y203 = 20 to 70
q/x02 = 0.15 to 4.0
h20/x02 = 15 to 60
m1oh/xo2 = 0.01 to 1.0
m2z/x02 = 0 to 2.0
Range 2(a)
X02/Y203 = 70 to 120
Q/X02 = 0.10 to 4.0
M2z/X02 = 0 to 2.0
if H20/X02 = 20 to 30
then Ml0H/X02 = 0.04 to 1.0
2 (b) ;
if H20/X02 = 30 to 40
then M10H/X02 = 0.1 to 1.0
2(c) :
if H2O/XO2 = 40 to 60
then M10H/X02 = 0.18 to 1.0
Range 3
xo2/y2°3 = 120 to 300
q/x02 = 0.05 to 4.0
m2z/x02 = 0 to 2.0
h20/x02 = 20 to 60
m10h/x02 = 0.08 to 1.0
12
Range 4
X02/Y203 = 300 to 800
Q/X02 = 0.02 to 4.0
M2Z/X02 = 0 to 2.0
H20/X02 = 10 to 70
m1oh/xo2 = 0 to 1.0
Range 5
x02/y203 = 800 to infinity (i.e. to no y203)
q/xo2 = 0.01 to 4.0
M2Z/X02 = 0 to 2.0
h2o/xo2 = 10 to 80
Ml0H/X02 = 0 to 2.0
The preferred polyalkylene polyamines are tri-
ethylene tetramine and tetraethylene pentamine.
Zeolite Nu-5 has a molar composition expressed by the formula:
0.5 to 1.5 R20 : Y203 : at least 10 X02 : 0 to 2000 H20
wherein R is a monovalent cation or -Vn of a cation of valency n, X is silicon and or germanium, y is one or more of aluminium,iron, chromium, vanadium, molybdenum, arsenic, manganese, gallium or boron, and H20 is water 25 of hydration additional to water notionally present when R is H, and has an X-ray pattern substantially as set out in Table 4 (as determined by standard technique using copper Ka radiation). Table 4 shows X-ray data for zeolite Nu-5.
Within the above definition of chemical com position, the number of moles of X02 is typically in the range 10 to 5000 and zeolite Nu-5 appears to be most readily formed in a state of high purity when the number of moles of X02 is in the range 45 to 100. 35 Zeolite Nu-5 may, be prepared by reacting an aqueous mixture comprising at least one oxide X02,
13
TABLE 4-
X-ray diffraction data for Nu-5
As-made Nu-5
Hydrogen Nu-5
dA
l00X/lo dA
loo^/io
11.11
70
11.12
85
.02
41
.04
51
9.96
37
9.96
45
9.74
18
9.75
9.00
3
8.95
3
8.04
1
.8.03
1
7.44
6
7. 43
4
7.08
3
7.08
3
6.71
7
6.71
8
6.36
14
6.37
.99
6.01
19
.70
12
.59
13
. 58
.13
4
.14
3
.03
6
.02
4.984
8
4.984
8
4.623
7
4.616
8
4.371
4. 370
14
4.266
4.266
14
TABLE 4 (contd)
i
X-ray diffraction data for nu-5
As-made Nu-5
Hydrogen Nu-5
dA
1001/lo dA
lOO1/lo
4.095
14
4.095
9
4.014
11
4 .022
12
3.859
100
3.859
100
3.821
70
3.825
68
3.749
39
3.755
32
3.725
54
3.731
48
3.643
31
3.652
28
3.598
4
3.601
4
3.484
7
3.484
6
3.358
3. 355
9
3.315
12
3.315
11
3.054
12
3.054
12
2.994
13
2.991
2.979
13
2.979
12
2.015
8
2 .015
1.996
8
1.994
at least one oxide and at least one compound selected from pentaerythritol, dipentaerythritol and tripentaery-thritol.
The reaction mixture preferably has the following 5 molar composition:
X02/^2°3 10 to 5000 preferably 50 to 200 MOH/XO2 0.01 to 0.5 preferably 0.10 to 0.25
0 to 5000 preferably 10 to 100 A/Y2O3 1 to 200 preferably 1 to 50
H2O/XO2 10 to 500 preferably 15 to 300
wherein X and Y are as above, M is an alkali metal or ammonium, A is the aforesaid pentaerythritol compound and Z" is a strong acid radical present as a salt of M and may be added as a free acid to reduce the free 0H~ 15 level to a desired value. M can be present as hydroxides or salts of inorganic or organic acids provided the MOH/XO2 requirement is fulfilled.
The preferred pentaerythritol compound is pentaerythritol, itself.
Zeolite Nu-6(2) has a molar composition expressed by the formula:
0.5 to 1.5 R20 : Y203 : at least 10 X02 : 0 to 2000 H20
wherein R is a monovalent cation or ^"/n of a cation of 25 valency n, X is silicon, and/or germanium, Y is one or more of aluminium, iron, chromium, vanadium, molybdenum, antimony, arsenic, manganese, gallium or boron, and H20 is water of hydration,additional to water notionally present when R is H, and has an X-ray diffraction pattern 30 substantially as set out in Table 5 (as determined by standard technique using copper Ka radiation).
1 99281
16
TABLE 5 ~ ZEOLITE Nu-6(2)
dA
8.41 6.67 6.09 4.61 4.33 ca 4.19 ca 4.10
looVio
45B 42 15B 27.5 100 shoulder
• -- - —•
dA
3.94
3.76
3.65
3.44
3.33
3.17
3.05
lOoVlo
2B
11B
15B
27 B
76
15B
9
Within the above definition of chemical composition, the 15 number of moles of X02 is typically in the range 10 to 5000 and zeolite Nu-6(2) appears to be most readily formed in a state of high purity when the number of moles of X02 is in the range 20 to 1000.
Zeolite Nu-6(2) may be prepared by heating 20 zeolite Nu-6(1) at a temperature in the range 200°C to 750°C, zeolite Nu-6(1) itself being made together with some zeolite Nu-6(2) by reacting an aqueous mixture containing at least one oxide X02, at least one oxide Y203 and a 4,4'-bipyridyl compound.
The reaction mixture preferably has the follow ing molar composition:
XO2/Y2O3 10 to 5000 preferably 20 to 3000
M0H/X02 0 to 1.0 preferably 0.01 to 0.3
Z~/Y203 10 to 5000 preferably 10 to 100
Q/Y203 0.1 to 5000 preferably 1 to 500
H20/X02 10 to 500 preferably 15 to 300
B0H/Y203 0 to 500,000 preferably 0 to 1000
wherein X and Y are as above, M is an alkali metal or ammonium, Q is the aforesaid 4,4'-bipyridyl compound 35 and Z~ is a strong acid radical present as a salt of M and may be added as a free acid to reduce the free
2 81
17
0H~ level to a desired value. M and/or Q can be present as hydroxides or salts of inorganic or organic acids provided the MOH/XO2 requirement is fulfilled. BOH is an aliphatic or aromatic alcohol, preferably an alkanol.
Whilst not essential, an alcohol improves crystallisation in viscous reaction mixtures.
The preferred bipyridyl compound is 4,4'-bipyridyl itself.
The preferred alcohol (BOH) is ethanol. 10 Zeolite Nu-10 has a molar composition expressed by the formula:
0.5 to 1.5 R20 : Y203 : at least 60 X02 : 0 to 200 H20 wherein R is a monovalent cation or ^-/n of a cation of valency n,' X is silicon, and/or germanium, Y is one or 15 more of aluminium, iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese, gallium or boron, and H20 is water of hydration additional to water notionally present when R is H, and has an X-ray pattern substantially as set out in Table 6 (as determined by standard technique 20 using copper Ka radiation).
18
TABLE 6 X-Ray Data of Zeolite Nu-10
d(A)
I
.95 ± 0.25
m-*s
8.80±0.14
w^ra
6.99 ± 0.14
w->-m
.41± 0.10
w
4.57 ± 0.09
w
4.38 ± 0.08
vs
3.69 ± 0.07
vs
3.63 ± 0.07
vs
3.48 ± 0.06
m-*-s
3.36 ± 0.06
w
3.31± 0.05
w
2.78 ± 0.05
w
2.53 ± 0.04
m
2.44 ± 0.04
w
2.37 ± 0.03
w
1.88 ± 0.02
w vs = 60 to 100 s = 40 to 60 m = 20 to 40 w = 0 to 20
1$
Within the above definition of chemical composition the number of moles of XC^ is typically in the range 60 to 500. Zeolite Nu-10 appears to be most readily formed in a state of high purity when the number of moles 5 of X02 is in the range 80 to 120.
Zeolite Nu-10 may be prepared by reacting an aqueous mixture containing at least one oxide XO2, at least one oxide ^0^ at least one polyalkylene poly amine having the formula:
N — [ (CH2)X— N—R3]y— (CH2) s N
where x is in the range 2 to 6 and y is in the range from 0 to 10/ an amine degradation product thereof, or a precursor thereof. In the polyamine, each of R^ 20 to R^, independently, represents hydrogen or a C^-Cg alkyl group. When y is from 2 to 6, the R3 substituents may be the same or different. When y = 0 then x = 2 to 5.
The reaction mixture preferably has the following molar ratios:
X02/Y203 = 60 to 500, preferably 70 to 200, most preferred 80 to 150 M"^0H/X02 = 10~8 to 1.0, preferably 10~® to 0.25, most preferred 10"^ to 0.15 H2O/XO2 = 10 to 200, preferably 15 to 60, most pre-30 ferred 30 to 50
Q/XO2 = 0.5 to 4, preferably 0.1 to 1.0, most pre ferred 0.2 to 0.5
2
M Z/XO2 = 0 to 4.0, preferably 0 to 1.0, most preferred 0 to 0.6
wherein X and Y are as above, M is an alkali metal or
2
ammonium or hydrogen, M is an alkali metal or ammonium
199281'
or hydrogen and can be the same as and Q is the aforesaid polyalkylene polyamine, amine degradation product thereof or a precursor thereof, or a related compound.
— 0
Z is a strong acid radical present as a salt of 5 and may be added as a free acid to reduce the free M"^0H level to a desired value.
The preferred polyalkylene polyamines are tri-ethylene tetramine and tetraethylene pentamine.
Zeolite EU-1 has a molar composition expressed 10 by the formula:
0.5 to 1.5 R20 : Y203 : at least 10 X02 : 0 to 100 H20 wherein R is a monovalent cation or 1/n of a cation of valency n, X is silicon and/or germanium, Y is one or more of aluminium, iron, gallium or boron, and H20 is 15 water of hydration additional to water notionally present when R is H, and has an X-ray pattern substantially as set out in Tables 7 and 8 (as determined by standard technique using copper Ka radiation). Table 7 shows X-ray data for zeolite EU-1 as prepared, and Table 8 20 shows X-ray data for zeolite EU-1 in the calcined Na-H form.
Within the above definition of chemical composition, the number of moles of X02 is typically in the range 10 to 500 and zeolite EU-1 appears to be most readily formed in 25 a state of high purity when the number of moles of X02 is in the range 20 to 300.
Zeolite EU-1 may be prepared by reacting an aqueous mixture comprising at least one oxide X02, at least one oxide Y203 and at least one alkylated derivative 30 of a polymethylene ot-w diamine having the formula:
R2^N+ (CH2)n —N+^ R5
R3^
R
4
21
199281
TABLE 7
Zeolite EU-1 as freshly prepared d CA)
I/Io
11.03
Very Strong
.10
Strong
9.72
Weak
6.84
Weak
.86
Very Weak
4.66
Very Strong
4.31
Very Strong
4.00
Very Strong
3.82
Strong
3.71
Strong
3.44
Medium
3.38
Medium
3.26
Strong
3.16
Very Weak
3.11
Very Weak
2.96
Very Weak
2.71
Very Weak
2.55
Weak
2.48
Very Weak
2.42
Very Weak
2.33
Very Weak
2.30
Very Weak
2.13
Very Weak
TABLE 8
Zeolite EU-1 in calcined Na-H form d (A)
I/Io
11.11
Very strong
.03
Very strong
9.78
Weak
7.62
Weak
6.84
Medium
6.21
Very Weak
.73
Weak
4.87
Very weak
4.60
Very strong
4.30
Very strong
3.97
Very strong
3.77
Strong
3.71
Weak
3.63
Very weak
3.42
Medium
3.33
Medium
3.27
Strong
3.23
Medium
3.15
Weak
3.07
Weak
2.93
Weak
2.69
Weak
2.63
Very weak
2.57
Very weak
. 2.51
, Weak
2.45
Very weak
2.41
Very weak
2.32
Very weak
2.29
Very weak
2.11
Very weak
23
an amine degradation product thereof, or a precursor thereof, wherein n is in the range from 3 to 12 and to Rg which may be the same or different, can be alkyl or hydroxyalkyl groups, containing from 1 to 8 carbon 5 atoms and up to five of the groups R^~Rg can be hydrogen, the mixture having the molar composition:
XO2/Y2O3 at least 10, preferably 10 to 150
0h""/x02 0.1 to 6.0, preferably 0.1 to 1.0
(M++Q)/Y203 0.5 to 100 10 Q/(M+ + Q) 0.1 to 1.0 h2o/xo2 1 to 100
wherein X and Y are as above, M is an alkali metal or ammonium, and Q is the aforesaid alkylated derivative of a polymethylene diamine, an amine degradation product 15 thereof, or a precursor thereof, or a related compound.
M and/or Q can be present as hydroxides or salts of inorganic or organic acids provided the 0H~/X02 requirement is fulfilled.
Preferred alkylated polymethylene diamine starting 20 materials include alkylated hexamethylene diamines,
especially methylated hexamethylene diamines, for example 1:6-n,n,n,nl,n^,n"^-hexamethyl hexamethylene diammonium salts (e.g. halide, hydroxide, sulphate, silicate, aluminate).
Zeolite EU-2 has a molar composition expressed by the formula:
0.5 to 1.5 R20 : Y203 : at least 70 X02 : 0 to 100 H20 wherein R is a monovalent cation or ^/n of a cation of valency n, X is silicon and/or germanium, Y is one or 30 more of aluminium, iron, gallium, or boron, and H2O is water of hydration additional to water notionally present when a is H, and has an X-ray pattern substantially as set out in Table 9 (as determined by standard technique using copper Ka radiation).
24
TABLE 9
Zeolite EU-2
Interplanar Spacings d (A)
Relative Intensity 100 I/Io
11.74
17
.13
14
6.33
7
.85
7
4.33
4.18
86
3.89
100
3.69
7
3.37
7
3.08
2.85
18
2.09
Within the above definition of chemical composition, the 25 number of moles of X02 is typically in the range 100 to 5000 and zeolite EU-2 appears to be most readily formed in a state of high purity when the number of moles of X02 is in the range 150 to 3000.
Zeolite EU-2 may be prepared by reacting an 30 aqueous mixture comprising at least one oxide X02, at least one oxide Y20^ and at least one alkylated derivative of a polymethylene a-w diamine having the formula:
R\ /R4
R2"7 N+— <CH2)~ N+^R5
R3 R6
which by our definition is Q2+ an amine degradation product thereof, or a precursor thereof, wherein n is in the range from 3 to 12, to Rg which may be the same or different, can be alkyl or hydroxyalkyl groups con-10 taining from 1 to 8 carbon atoms and up to five of the groups R-j^-Rg can be hydrogen, the mixture having the molar composition:
x02/Y203 at least 70, preferably at least 150
0H~/X02 0.1 to 6.0 preferably 0.1 to 1.0
(M++Q)/Y203 0.5 to 100 Q/(M+ + Q) 0.1 to 1.0
h2o/xo2 1 to 100
wherein X and Y are as above, M is an alkali metal or ammonium and Q is the aforesaid alkylated derivative of 20 a polymethylene diamine, an amine degradation product thereof, or a precursor thereof, or a related compound.
M and/or Q can be present as hydroxides or salts of inorganic or organic acids provided that 0H~"/X02 requirement is fulfilled.
Preferred alkylated polymethylene diamine starting materials include alkylated hexamethylene diamines, especially methylated hexamethylene diamines, for example 1:6-N,N,N,N^,N1,Nl-hexamethyl hexane-1,6-diammonium salts (e.g. halide, hydroxide, sulphate, 30 silicate, aluminate).
Zeolite FU-9 has a molar composition expressed by the formula:
0.5 to 1.5 r20 : y203 : 15 to 30 x02 : 0 to 500 h20 wherein r is a monovalent cation or 1/n of a cation of 35 valency n, x is silicon and/or germanium, y is one or more of aluminium, iron, chromium, vanadium, molybdenum,
26
arsenic, manganese, gallium or boron, and H^O is water of hydration additional to water notionally present when R is H, and having an X-ray pattern substantially as set out in Table 10 (as determined by standard technique 5 using copper Koi radiation). Table 10 shows X-ray data for zeolite FU9 as prepared.
Zeolite FU9 may be prepared by reacting an aqueous mixture comprising at least one oxide X02, at least one oxide ^2^3 an<^ leas^ one tetramethylammonium compound. 10 The reaction mixture preferably has the following molar composition:
XO2/Y2O2 5 to 50 preferably 10 to 30
free MO2/XO2 0.1 to 1.0 preferably 0.1 to 0.5
Z-/Y2O3 0 to 5000 preferably 10 to 100
Q/Y2O2 0.1 to 150 preferably 1 to 50
H2O/XO2 5 to 200 preferably 10 to 30
Q = (TMA)2 + xA
wherein X and Y are as above, M is an alkali metal or ammonium, and Q is a mixture of TMA the tetramethylammonium 20 compound, amine degradation product thereof or a precursor thereof, or a related compound, and A which is a trialkyl-amine and/or an alkanolamine or salt thereof, where x is equal to 0.2 to 2.0 moles and A preferably contains 1 to 12 carbon atoms. Z~ is a strong acid radical present as 25 a salt of M and may be added as a free acid to reduce the free £^0 level to a desired value. M and/or Q can be present as hydroxides or salts of inorganic acids provided the M2O/XO2 requirement is fulfilled.
The preferred quaternary compound is a tetra-30 methyl ammonium hydroxide.
For the efficient use of the reactants in methyl t-butyl ether production, it is important that any catalyst for the vapour phase reaction does not promote by-product formation. By virtue of its unique crystal 35 structure, the channel system in our preferred zeolite,
TABLE 10
dA
11.3
9.5
7.05
6.99
6.61
.77
.67
4.97
4.84
4.75
lOO1/!©
7
100
21
22
19
13
3
8
1
2
dA
4.57
3.99
3.94
3.85
3.78
3.66
3.56
3.53
3.49
3.38
lOO^/Io
2
52
37
18
32
14
40
55
52
dA
3.31
3.14
3.05
2.950
2.898
2.713
2.643
2.617
2.575
2.545
lOoVlo
21
8
9
3
4
1
3
1
dA
2. All
2.414
2.347
2.308
2.260
2.150
2.109
2.027
1.998
loo1/!©
3
2
3
1
1
2
2
2
6
to
-j
28
Nu-10, limits the formation of oligomers of isobutene.
Thus, a very high proportion of isobutene is converted to metyl t-butyl ether.
The invention is illustrated by the following 5 Examples.
Examples 1-7
These examples illustrate the preparation of zeolite Nu-2 and its use as a catalyst in the production of methyl t-butyl ether (MTBE) from isobutene and methanol. 10 The synthesis mixture for the preparation of zeolite Nu-2 had the following molar composition:
1.35 Na20, 3.14 Q20, Al203, 29 Si02, 311 H20 8.7g solid sodium hydroxide were dissolved in 250g tetra ethyl ammonium hydroxide (40% aqueous solution) followed 15 by 16.4g Kaiser SA alumina powder. Next 649g colloidal silica were added with stirring. The resulting gel/slurry was crystallised to zeolite Nu-2 in a stirred autoclave after 6 days at 150°C. The washed dried product had the molar composition:
0.6 Na20, 2.2 Q20, A1203, 20Si02, 6 H20
The product thus obtained was calcined at 450°C for 48 hours, followed by treating with normal hydrochloric acid for 2 4 hours, washing thoroughly with deionised water and calcined for 24 hours at 450°C. The product was 25 zeolite H-Nu-2.
ml of methanol (0.5 mole) and lg of Nu-2 zeolite (prepared as above) were added to a glass flask in a stream of nitrogen. 20 ml (0.21 mole) of isobutene was condensed into the cooled flask. The mixture was 30 put into an autoclave then heated with stirring at 90°C for one hour. After the reaction the autoclave was cooled to 0°C and the reaction mixture was analysed by gas chromatography.
The results are shown as Example 1 in Table 11 35 are as follows:
29
Mole % conversion of isobutene 92.3 Mole % conversion of methanol 39.4 Selectivity toMTBE 98.0
The procedure described for Example 1 was 5 used in Examples 2-7. The results are also shown in Table 11.
Example
Catalyst
Si02/Al203 Ratio
Catalyst Cone %
Temp oc
Time hr
CH3OH/ Isobutene mole ratio
Mole % Conversion
Selectivity to M T B E
Isobutene
Methanol
1
Nu-2
3.6
90
1
2.4
92.3
39.4
98.0
2
Nu-2
0.9
90
1
2.4
89.5
38.2
99.0
3a
Nu-2
3.6
90
1
2.4
84.8
36.1
98.5
4b
Nu-2
3.6
90
1
2.4
82.0
.0
98.4
i 5
Nu-2
3.6
50
6
2.4
76.5
32.9
97.5
6
Nu-2
3.6
50
18
2.4
87.8
38.6
98.3
7
Nu-2
4.4
18
1.8
66.0
37.3
97.0
8
ZSM-5
80
3.6
90
1
2.4
41.8
17.9
92. 3
9
ZSM-5
80
3.6
50
18
2.4
53.5
23.0
93.5
FU1
28
3.6
90
1
2.4
16.5
7.2
89.0
11
EU1
42
3.6
90
1
2.4
.3
2.2
46.0
12
ZSM-35
3.6
90
. 1 i
2.4
29.6
12.7
69.7
13
EU2
150
3.6
90
1
2.4
.0
12.8
96.5
14
EU2
150
1
3.6
50
18
2.4
54.5
23.2
92.6
Nu-4
40
3.6
90
1
2.4
28.4
11.9
88. 5
00
O
TABLE 11 continued
Example
Catalyst
Si02/Al203 Ratio
Catalyst Conc %
Temp °C
Time hr
CH3OH/ Isobutene mole ratio
Mole % Conversion
Selectivity to M T B E
Isobutene
Methanol
16
Zeolite
19
3.6
90
1
2.4
87.0
37.2
97.5
Beta
1
17
FU9
11
3.6
90
1
2.4
8.5
3.6
87.8
18
j
Nu-6(2)
51
3.6
90
1
2.4
6.0
3.6
78.3
Notes
(a) Under 50 atmos of CO2
(b) In the presence of 20 ml of hexane as solvent
(c) Catalyst conc = Wt of catalysts , on
199281
32
Referring to Table 11, Examples 1-7 illustrate the use of zeolite Nu-2 as catalyst for the production of MTBE from isobutene and methanol.
Example 1 shows the high conversion and select-5 ivity to MTBE in a short reaction time (1 hour) and at 90°C.
Example 2 demonstrates that a lower concentration of catalyst can be used without adversely affecting conversion and selectivity.
Example 3 shows that the reaction can be carried out under high pressure in the presence of an inert diluent (carbon dioxide), with only slight reduction in conversion and selectivity.
Example 4 shows that the reaction can be carried 15 out in the presence of an inert solvent (hexane) with only slight reduction in conversion and selectivity.
Examples 5-7 show the reaction can be carried out at much lower temperature, although the reaction time is increased.
Examples 8-18
These examples illustrate the production of methyl t-butyl ether (MTBE) from isobutene and methanol using a range of zeolites as catalysts. The preparation of the zeolites is described in the relevant patent specifications 25 (to which reference has already been made). The as-made zeolites were calcined and exchanged and calcined as described in Example 1.
The results, shown in Table 11, illustrate that zeolite beta (Example 16) and zeolite Nu-(2) (Examples 30 1-7) are the most effective catalysts.
Example 19
This example illustrates the production of ethyl t-butyl ether (ETBE) from isobutene and ethanol.
ml of ethanol (0.5 mole) and lg of Nu-2 zeolite ^35 were added to a glass flask in a stream of nitrogen. 20 ml (0.21 mole) of isobutene was condensed into the cooled flask. The mixture was put into am autoclave then heated
33
with stirring at-90OC for one hour. After the reaction the autoclave was cooled to 0°C and the reaction mixture was analysed by gas chromatography. The results were as follows 5 Mole % conversion of isobutene 65.5
Mole % conversion of ethanol 43.3 Selectivity to ETBE 97.0
Example 20
This example illustrates the production of methyl 10 3-methylpentyl ether (M3MPE) from 3^methylpent-2-ene and methanol using zeolite Nu-2 as catalyst.
ml of methanol (0.25 mole), 10 ml of 3-methylpent-2-ene (0.082 mole) and lg Nu-2 zeolite were added to a glass flask in a stream of nitrogen. 15 The mixture was put into an autoclave then heated to 90°C for one hour. After the reaction the autoclave was cooled to 20OC and the reaction mixture was analysed by gas chromatography.
The results were as follows:-20 Mole % conversion of 3-methyl-2-pentene 21.2
Mole % conversion of methanol 7.7
Selectivity to M3MPE 94.5
Example 21
This example illustrates the production of ethylene 25 glycol methyl t-butyl ether (EGMTBE) from isobutene and 2-methoxyethanol using zeolite Nu-2 as catalyst.
ml of 2-methoxyethanol (0.25 mole), 20 ml of isobutene (0.21 mole) and 0.25 g Nu-2 zeolite were added to a glass flask in a stream of nitrogen. The 30 mixture was put into an autoclave then heated to 90°C for one hour. After the reaction, the mixture was analysed by gas chromatography.
The results were as follows:-
Mole % conversion of isobutene 42.3
Mole % conversion of 2-methoxyethanol 36.6
Selectivity to EGMTBE 96.5
34
Examples 22-24
1 gm of Nu-2 zeolite was powdered and packed into a glass tube. The tube and contents were heated by a furnace to 90°C whilst passing a continuous stream 5 of methanol vapour and isobutene over the zeolite bed (mole ratio 2:1). The products from the reaction were collected at hourly intervals and analysed by gas chromatography.
The results, shown as Example 22 in Table 12, 10 are as follows:-
Selectivity to MTBE ~ 65-80%
Selectivity to Di-isobutene 20-30%
Catalytic activity (g MTBE/g catalyst/hr)
0.06-0.12
The procedure described for Example 22 was used in Examples 23 and 24 except that the temperature was lowered to 70°C then 50°C as shown in Table 12. Examples 22-24 demonstrate that selectivity to MTBE increases as the temperature is lowered.
Example 25 _ ' _ _
lg of zeolite Nu-2 prepared as described in Example 1 was soaked in the bulky amine phenanthridine (20 ml) for 24 hours then filtered, washed well with hexane and dried on a vacuum line at 100°C. The amine treated 25 zeolite was then packed into a glass tube as described in Example 22 and evaluated for the synthesis of MTBE in a flow reactor at 90°C.
The results are shown in Table 12 and demonstrate that at 90°C the bulky amine ion-exchanged onto the 30 surface of the zeolite inhibits the formation of di-isobutene and- improves the overall selectivity to MTBE without loss in catalyst activity.
Examples 26-30
These examples illustrate the production of methyl 35 tertiary butyl ether from isobutene and methanol using a range of zeolites in the flow reactor. The
TABLE 12
Example
Catalyst
Si02/Al203 ratio
Temp °C
MeOH Isobutene mole ratio
Selectivity to MTBE %
Selectivity to Di-isobutene %
Activity g MTBE/ g cat/hr.
22
Nu-2
90
2
65-80
-30
0.06-0.12
23
Nu-2
70
2
85-95
0-5
0.08-0.13
24 i 25 26
Nu-2
Nu-2/phenan-thridine
Beta
20 19
50 90 90
2 2 2
90-95 80-90 60-75
0-5 10-20 20-35
0.04-0.08 0.06-0.12 0.04-0.08
27
Nu-10
90
90
2
85-95
-15
0.06-0.09
28
Nu-4
40
90
2
80-90
-15
0.04-0.07
29
Nu-4
40
70
2
95-100
0-5
0.10-0.12
ZSM-5
80
90
2
85-95
0-10
0.02-0.06
Claims (9)
1. A process for the production of an ether which comprises contacting an olefin and an alcohol with a catalyst comprising a zeolite having an XO2/Y2O3 ratio equal to or greater than 10f wherein X is silicon and/ or germanium and Y is one or more of aluminium/ iron, chromium, vanadium, molybdenum, arsenic, manganese, gallium or boron, the zeolite being predominantly in the hydrogen form.
2. A process according to claim 1 wherein the zeolite has been treated with a bulky organic base.
3. A process according to claim 1 or claim 2 wherein the olefin is a mono- or di-olefin containing from 4 to 16 carbon atoms.
4. A process according to claim 3 wherein the olefin contains 4 to 9 carbon atoms.
5. A process according to any one of the preceding claims wherein the alcohol is a primary or secondary alkanol containing from 1 to 12 carbon atoms.
6. A process according to claim 5 wherein the alcohol contains from 1 to 4 carbon atoms.
7. A process according to any one of claims 1 to 4 wherein the alcohol is an ether alcohol of the formula: R0(ch2ch20)nH wherein R is H or hydrocarbyl and n is 1-20.
8. A process according to any one of claims 1 to 6 wherein isobutene and methanol are reacted to form methyl t-butyl ether.
9. A process according to any one of the preceding claims wherein the zeolite is selected from zeolites Nu-2, Nu-4, Nu-10 and beta. DATED THiS DAY OF A. J. PARK & SON PER AGENTS FOR THE APPLICANTS
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8040779 | 1980-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NZ199281A true NZ199281A (en) | 1986-05-09 |
Family
ID=10518107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NZ199281A NZ199281A (en) | 1980-12-19 | 1981-12-15 | Production of an ether from an olefin and an alcohol using zeolite catalyst |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0055045B1 (en) |
| JP (1) | JPS57131733A (en) |
| AU (1) | AU543927B2 (en) |
| DE (1) | DE3166088D1 (en) |
| DK (1) | DK564581A (en) |
| NZ (1) | NZ199281A (en) |
| ZA (1) | ZA818682B (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN157506B (en) * | 1981-01-08 | 1986-04-12 | British Petroleum Co | |
| US5248841A (en) * | 1982-04-30 | 1993-09-28 | Mobil Oil Corporation | Hydrocarbon conversion with ZSM-22 zeolite |
| US4584415A (en) * | 1982-09-29 | 1986-04-22 | Standard Oil Company (Indiana) | Formation of alkyl ethers from alcohols and alkenes using AMS-1B crystalline borosilicate |
| US4481177A (en) * | 1982-12-09 | 1984-11-06 | Mobil Oil Corporation | Synthesis of zeolite ZSM-22 with a heterocyclic organic compound |
| GB8518026D0 (en) * | 1985-07-17 | 1985-08-21 | British Petroleum Co Plc | Chemical process |
| US4714787A (en) * | 1985-09-03 | 1987-12-22 | Mobil Oil Corporation | Production of ethers from linear olefins |
| US5225609A (en) * | 1991-12-17 | 1993-07-06 | Mobil Oil Corporation | Production of tertiary alkyl ether using improved zeolite catalyst |
| WO1994019304A1 (en) * | 1987-09-25 | 1994-09-01 | Mobil Oil Corporation | Production of alkyl tertiary alkyl ethers |
| US4826507A (en) * | 1987-12-08 | 1989-05-02 | Mobil Oil Corporation | Integrated etherification and oxygenates to gasoline process |
| JP2786217B2 (en) * | 1987-12-30 | 1998-08-13 | モービル・オイル・コーポレイション | Olefin contact watering method |
| US4857664A (en) * | 1987-12-30 | 1989-08-15 | Mobil Oil Corporation | Process for the production of ether and alcohol |
| US4962239A (en) * | 1988-10-06 | 1990-10-09 | Mobil Oil Corp. | Process for preparing ethers |
| US4886918A (en) * | 1988-11-07 | 1989-12-12 | Mobil Oil Corporation | Olefin hydration and etherification process employing serially staged olefin introduction |
| US5178748A (en) * | 1988-12-22 | 1993-01-12 | Imperial Chemical Industries | Catalytic reactions using zeolites |
| GB8829923D0 (en) * | 1988-12-22 | 1989-02-15 | Ici Plc | Zeolites |
| US4935552A (en) * | 1989-01-12 | 1990-06-19 | Mobil Oil Corporation | Dual stage process for the production of ethers |
| US4927977A (en) * | 1989-01-12 | 1990-05-22 | Mobil Oil Corporation | Process and apparatus for the uniform distribution of a two-phase feed in a chemical reaction zone |
| US5144084A (en) * | 1989-01-12 | 1992-09-01 | Mobil Oil Corporation | Process for the conversion of olefins to alcohols and/or ethers |
| US5071627A (en) * | 1989-12-04 | 1991-12-10 | Mobil Oil Corp. | Reactor system for conducting a chemical conversion |
| CA2097090A1 (en) * | 1992-06-02 | 1993-12-03 | Quang N. Le | Process for the production of tertiary alkyl ether rich fcc gasoline |
| ES2127909T3 (en) * | 1993-10-15 | 1999-05-01 | Fina Research | GLYCEROL ETHER PRODUCTION PROCEDURE. |
| US5600045A (en) * | 1993-12-02 | 1997-02-04 | The Dow Chemical Company | Process for conversion of crude hydrocarbon mixtures |
| AU702870B2 (en) † | 1995-06-08 | 1999-03-11 | Nippon Shokubai Co., Ltd. | Process for production of (poly)alkylene glycol monoalkyl ether |
| US6057486A (en) * | 1997-12-22 | 2000-05-02 | Institut Francais Du Petrole | Catalyst containing a zeolite EUO and the use of the catalyst in a process for isomerizing aromatic compounds containing 8 carbon atoms per molecule |
| EP0923987A1 (en) * | 1997-12-22 | 1999-06-23 | Institut Français du Pétrole | Catalyst comprising a zeolithe EUO and its use in the isomerisation of aromatic C8 compounds |
| FR2772642B1 (en) * | 1997-12-22 | 2000-01-28 | Inst Francais Du Petrole | CATALYST CONTAINING A EUO STRUCTURAL TYPE ZEOLITE |
| EP3398928B1 (en) * | 2015-12-28 | 2021-01-20 | Zeon Corporation | Method for producing cyclopentyl alkyl ether compound |
| CN105944754A (en) * | 2016-05-24 | 2016-09-21 | 山东成泰化工有限公司 | Light oil etherification catalyst and preparation method thereof |
| CN109092346B (en) * | 2017-06-20 | 2023-03-10 | 高化学株式会社 | Catalyst for preparing methoxyethyl tert-butyl ether by reacting ethylene glycol monomethyl ether with isobutene, and preparation method and application thereof |
| WO2021067087A1 (en) * | 2019-09-30 | 2021-04-08 | Dow Global Technologies Llc | Methods of etherification |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1520726A (en) * | 1975-07-23 | 1978-08-09 | Standard Oil Co | Liquid phase process for the manufacture of methyl tertiary alkyl ethers |
| CS189071B1 (en) * | 1977-01-17 | 1979-04-30 | Vendelin Macho | Process for preparing ethers and/or etheralcohols |
| ZA815144B (en) * | 1980-08-01 | 1983-03-30 | British Petroleum Co | Method for promoting the activity of cation-exchangeable layered clay and zeolite catalysts in proton-catalysed reactions |
-
1981
- 1981-12-04 DE DE8181305734T patent/DE3166088D1/en not_active Expired
- 1981-12-04 EP EP81305734A patent/EP0055045B1/en not_active Expired
- 1981-12-14 ZA ZA818682A patent/ZA818682B/en unknown
- 1981-12-15 NZ NZ199281A patent/NZ199281A/en unknown
- 1981-12-18 DK DK564581A patent/DK564581A/en not_active Application Discontinuation
- 1981-12-18 AU AU78660/81A patent/AU543927B2/en not_active Ceased
- 1981-12-18 JP JP56205053A patent/JPS57131733A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3166088D1 (en) | 1984-10-18 |
| JPH0424339B2 (en) | 1992-04-24 |
| DK564581A (en) | 1982-06-20 |
| AU7866081A (en) | 1982-06-24 |
| ZA818682B (en) | 1983-01-26 |
| AU543927B2 (en) | 1985-05-09 |
| JPS57131733A (en) | 1982-08-14 |
| EP0055045B1 (en) | 1984-09-12 |
| EP0055045A1 (en) | 1982-06-30 |
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